MONTE CARLO SIMULATION OF H2O-CO2 MIXTURES TO 1073.15 K AND 30 KBAR

Abstract

The thermodynamic and structural properties of H2OCO2 mixtures along two supercritical isotherms at 773.15 and 1073.15 K in the pressure range from 0.2 to 30 kbar have been investigated by the NVT and NPT Monte Carlo method using the TIP4P and MSM3 effective intermolecular potentials for H2O and CO2, respectively. Calculated excess volumes of mixing are in very good agreement with experimental data at low pressure. Results suggest that non-ideal mixing still occurs at 1073.15 K and at pressures up to 7 kbar. Although structural analysis shows that there is some clustering of H2O molecules in the mixtures relative to the pure fluids, this does not' appear to correlate with excess volumes. The most pronounced clustering occurs at high pressure and low temperature while the largest excess volumes occur at low pressure and low temperature.An equation is given to calculate excess volumes of mixing at different pressures and compositions along both isotherms. It has the following mathematical expression: Vex = [a1XCO2(1 − XCO2) + b1XCO2ln(XCO2)]a +bP + cP + dP + eP2 + ƒP2 and reproduces calculated Vex with a standard deviation of 0.8 and 0.4 cm3/mol at 773.15 and 1073.15 K, respectively.